WORK OF THE INSTITUTE OF PHYSICAL CHEMISTRY IMENI L. V. PISARZHEVSKIY, ACADEMY OF SCIENCES UKRAINIAN SSR

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• Document Page Count: 12
• Document Creation Date: December 22, 2016
• Document Release Date: August 31, 2011
• Sequence Number: 126
• Publication Date: September 30, 1954
• Content Type: REPORT

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WORK OF THE INSTITUTE OF PHYSICAL CHEMISTRY IMEM L. V. PISARLHEVSKIY
ACADEMY OF SCIENCES UKRAINIAN SSR
U &1 ]almicheskiy Zhu .:Vol 20, No 2, pp 169-181
Kiev, may 1954
The research chair of electronic chemistry, which was organized by L. V.
Pisarzhevskiy at Dnepropetrovsk in 1922, expanded rapidly. In 1927 this chair
was transformed into the Institute of Physical Chemistry, which was included
in 1936 into the organization of the Academy of Sciences Ukrainian SSR, and
was named after its founder in 1938. The Institute of Physical Chemistry imeni
Pisarzhevskiy was the first chemical research institution in the Ukraine and
the first physicochemical institute in the USSR.
During its whole existence the institute has worked in close collabora-
tion with the scientific institutions of the other Union republics, primarily
the institutes of the Academy of Sciences USSR. For a number of years the in-
stitute was the principal center of the development and dissemination of the
new electronic theories in chemistry, which have now been firmly inculcated
into Soviet science. More than 800 publications, most of them contributions
to All-Union scientific periodicals, have originated at the institute. The
institute has also published a number of monographs and textbooks. A series
of meetings and All-Union conferences of physical chemistry, in which the most
prominent Soviet chemists participated, were held at the institute. Currently
the institute maintains close contacts with a number of USSR scientific insti-
tutions and conducts investigations in collaboration with some of them.
The scientific basis of the Institute of Physical Chemistry was formed by
the important chemical school created by L. V. Pisarzhevskiy, who in 1914 ex-
plained the fundamental chemical processes, problems of valency, various as-
pects of the structure of chemical compounds, and other chemical phenomena
from the standpoint of electronic concepts. Subsequently, Pisarzhevskiy and
members of his group further developed the electronic theory. On the basis of
this theory they explained redox processes, processes which take place in elec-
trical batteries, and the structure of many organic and inorganic compounds.
Pisarzhevskiy's successors are continuing to work along these lines at the In-
stitute of Physical Chemistry imeni Pisarzhevskiy, which has become one of the
basic physicochemical institutions of the USSR.
Brief reviews of the work done by the institute in various fields follow.
Work in Theoretical and A lied Electrochemistry
Until the end of the nineteen thirties, electrochemistry occupied an im-
portant place in the work of the institute.
his To investigate the state of electrolytes in solution, A. I. Brodskiy and
cF. I. Trakhtenberg, andiothers) Lapplied hoptical rand electrochemical A
Zak, meth-
ods between 1927 and 1934. An interferometric method was developed at the in-
stitute by means of which the ionic refractions in very dilute solutions could
be measured directly. It was found that these refractions are additive in the
case of strong electrolytes, i.e., that strong electrolytes are dissociatedcom-
pletely in very dilute solutions. This disproved the results of Fajans, who
measured refractions in concentrated solutions and found on extrapolation to
high dilutions that the refractions in the case of strong electrolytes were not
additive. FaJans concluded that dissociation of strong electrolytes in dilute
solutions is not complete. In other work done at the institute, Raman spectra
were used to determine the degree of association of ions and molecules in solu-
tion. In mixtures of trichlorides of the elements of the 5th group, no associa-
tion products were found. On the other hand, there was displacement of frequencies
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brought about by the interaction of polar solvents with the dipols formed by
the molecules of the dissolved trichlorides. In a series of investigation
the applicability of the Deb
H
ye??
s
ueckel theory under various conditions was
critically examined and its validity for nonaqueous solutions proved in a num-
ber of cases.
A. I. Brodskiy's theory of the dependence of electrode potentials and
equilibrium constants of ionic reactions on the nature of the solvent was
checked on mercury and quinhydrone circuits and found applicable. A general
theory of quinhydrone and quinone-hydroquinone electrodes was developed and
found in agreement with experimental data. More precise values of the solubil-
ity products of a number of mercurous salts were obtained. The diatomic struc-
ture of the mercuro-ion was definitely proven. The formula which establishes
the linear dependence of electrode potentials and of the equilibrium constant
on the inverse value of the dielectric constant of the solvent, and which ex-
presses a relationship that had been derived earlier in a simplified manner on
the basis of the theory mentioned above, was proven in a more rigorous fashion
under considration of the diffuse structure of the double electric layer. This
formula was later also obtained by Bjerrum and usually bears his name. It has
been applied frequently since then in research on the following subjects: the
dependence between the nature of the solvent and the chemical activities of the
solutes, the strength of acids and bases, the equilibrium constants of ionic re-
actions and tautomeric transformations, electrode potentials, polarographic curves,
etc.
The work on the thermodynamics of solutions that was carried out at the in-
stitute was a continuatiod of research on the subject done by Pisarzhevskiy.
'Between 19,19 and 1941 I. G. Ryss studied the thermodynamics of complex com-
pounds of fluorine with boron and silicon in solutions. Particular attention was
paid to the equilibria of hexafluorosilicates and to the kinetics of their decom-
position.
A second line of electrochemical research, which was pursued by a group of
workers headed by V. A. Royter and in which V. A. Yuz and others participated,
dealt with the study of nonequilibrium electrode processes. The theory of the
delayed discharge of hydrogen ions, which had been developed by a number of in-
vestigators, could not he applied without difficulty to the discharge of metal
ions. A new oscillographic method was applied at the institute. The interpre-
tation of the oscilograms and of the kinetic curves led to the conclusion that
the fundamental mechanism of the processes taking place at metal electrodes is
identical with that of processes taking place at the hydrogen electrode.
tion withwathes concorddesthat the ospetelileficeryesftfaectsatttuikeingofplactealisn
occurebe-
cause of the differences in the work of activation produced by differences in the
,d, eS.Lbf orderly arrangement within individual crystal surface areas. The work .
in question furnished the basis for the formulation of a unified theory of elec-
trode processes that applies both to as el
t
ec
rodes and metal electrodes. The
contradictory results Obtained 'in former work were caused by inaccuracies for
which inadequate consideration of changes in the surface area of the
electrodes
and of differences in the a_tivity of the electrodes at different current densi-
ties was responsible. A method was developed which made it possible to measure
the changes involved and by taking them into consideration determine experimen-
tally the value of specific velocities of the discharge of ions and the formation
of ions at electrodes under equilibrium conditions.
Evaluation of the results obtained tide it possible to bring further preci-
sion into the determination of the role which microfactors and macrofactors play
in the electrodepoittion of metals and their electrolytic dissolution.
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In the field of applied electrochemistry work was done principally on corro-
sion. During 1938-191+1, A. S. Afanas'yew subjected to critical study the methods
used in the laboratory determination of the corrosion stability of iron and pro-
posed new, improved methods. Furthermore, the electrochemical processes involved
in corrosion were investigated and improved methods were proposed for the pickling
of Cromansil [chromium-manganese-silicon steel] pipes and wire at metallurgical
plants (A. S. Fomenko, I. S. Novosel'skiy, and others).
Before World War II the work done by the institute in the field of the elec-
trochemistry of solutions represented a major portion of work done in this field
in the USSR. Both All-Union physicochemical conferences devoted to electrochem-
istry (the 5th in 1929 and the 12th in 1935) were held at the institute. The
first conference dealt principally with the state of dissolved electrolytes,
while the second was devoted to the interaction of dissolved substances with the
solvents and the effects which these substances have on the properties of the solu-
tions.
Work on Catalysis and A sorption
Work in the field of catalysis has been one of the principal activities of
the institute since its foundation.
Between 1924 and 1938 Pisarzhevskiy and his collaborators created the elec-
tronic theory of catalysis, according to which interaction between two different
species of molecules at a catalyst which exhibits metal conductivity takes place
through the interaction of molecules of one of the two species with the free elec-
trons, so that active radicals are formed. In addition to considering chemical
properties, Pisarzhevskiy's theory pays considerable attention to the following
properties of catalysts: electrical conductivity, parameters of the crystal lat-
tice, presence of uncompleted electron shells in the atoms of the catalyst, and
the work performed to bring about the escape of an electron. The possibility
that light may affect adsorption and catalysis is.also taken into consideration
by this theory.
At the time when Pisarzhevskiy proposed his theory of catalysis, this theory
was far in advance of the contemporary state of knowledge. Only in recent years
has the electronic theory of heterogeneous catalysis been revived through the
work of S. Z. Roginskiy, a former pupil of Fisarzhevskiy who is head of the fore-
most school of catalysis in the USSR, and F. F. Vol'kenshteyn. Their views on
the nature of catalysis are close to those held by N. N. Semenov and others.
The concepts of Pisarzhevskiy's theory were checked on two model reactions:
the formation of water from hydrogen and oxygen, and the decomposition of hydro-
gen peroxide.
At Pisarzhevskiy's initiative, work on the kinetics and mechanism of other
catalytic reactions was started at the institute in 1933. The work done by V. A.
Royter and his collaborators (M. T. Rusov, M. Ya. Rubanik, I.'A; Khrizman, G. P.
Korgeychuk, and others) in this field was particularly prolific:-'this group in-
vestigated the synthesis and decomposition of ammonia, the conversion of carbon
monoxide, the selective oxidation of hydrogen sulfide, the oxidation of carbon
monoxide, of acetylene, and-of sulfur dioxide, the incomplete oxidation of olefins
and of naphthalene, etc. In addition to the kinetics of processes involved in ca-
talysis, the adsorption of the reacting gases and the mechanism of catalysis were
studied. In research on the adsorption of hydrogen and nitrogen at iron catalysts
and iron-ammonia catalysts, it was established that the rate of the activated ad-
sorption of nitrogen at the catalyst is equal to the rate of synthesis of ammonia,
i.e., the rate of the adsorption of nitrogen determines the over-all velocity of
the process. New methods for determining the surface area of ammonia catalysts
and their permeability to gases were developed. Ways were found for eliminating
harmful side reactions which occur in the catalytic oxidation of hydrogen sulfide
in the presence of hydrogen.
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series Investigations was clarification of the important role that transferphenomenaoplayn v
in the ac-
tion of porous industrial catalysts. The fact was demonstrated that the influ-
ence of transfer phenomena had been underestimated before, and methods were de
veloped which made it possible to determine experimentally the effect produced
by these phenomena. As a result, a theory of the kinetics of processes taking
place at porous catalysts was developed. Application of this theory to the proc-
esses under investigation led to improvements in the efficiency and selectivity
of industrial catalysts. In the course of this work, the true kinetics of the
catalytic processes in question, which are usually obscured by macrokinetic fac-
tors, were elucidated. The processes of ammonia catalysis were investigated in
particular detail.
Many of the results obtained in theoretical investigations of this type
were applied in industrial work. The research done by the institute has contri-
buted in a considerable measure to the fact that macrofactors are considered
widely in work on catalytic phenomena done by Soviet specialists in this field.
For the first time, the idea that intermediate compounds are formed in the
course of oxidative catalytic processes that take place in the presence of metal
oxides was subjected to a direct experimental check (F. M. Vaynshteya and G. Ya.
Turovskiy). It was shown that during the catalytic oxidation of carbon monoxide
with oxygen in the presence of copper oxide, or manganese dioxide, there is no
exchange between the oxygen of the metal oxides and the oxygen of the gas phase.
This refuted the widely held view that there is alternate reduction and oxidation
of the catalyst during catalysis.
Another line of research on catalysis which received considerable develop-
ment at the institute pertains to heterogeneous-homogeneous catalysis. The most
important result of the research activities in this field, which are headed by
M. V. Polyakov, has been creation of an experimental basis for the theory of
heterogeneous-homogeneous catalysis, i.e., a theory which united into one system
chain-radical and catalytic reactions. The theory in question was originally
formulated by Polyakov in connection with a study of the kinetics of the decom-
position of potassium chlorate mixed with manganese dioxide, and of the ignition
of the explosive hydrogen-oxygen mixture in the presence of platinum or palladium.
According to this theory, homogeneous gas reactions originate under heterogeneous
conditions, while heterogeneous reactions are transformed either into homogeneous
reactions proceeding in stages or into chain-radical processes.
To confirm the correctness of these views, several series of investigations
were carried out.
The first group of these investigations dealt with processes of incomplete
and slow cata~ytic combustion, and incomplete explosive combustion. The method
of igniting the mixture by means of an incandescent filament and capturing the
intermediate products (peroxides, aldehydes, etc.) at a low temperature was used.
In this work, the heterogeneous-homogeneous nature of the formation of the inter-
mediate products was proven for the first time.
A long series of subsequent investigations dealt with the kinetics and mech-
anism of the slow and the explosive combustion of hydrogen, methane, carbon mon-
oxide, and other substances. The effects exerted on the velocity of these reac-
tions by the nature and state of the surface of the walls, by catalyst poisons,
and by platinum rods of different lengths were studied at the institute. It was
established that the dependence of the kinetics of these reactions on the nature
and state of the walls of the vessel is due to the origination and interruption
? of chains at the surface of the walls. This result directly confirms the opera-
tion of a heterogeneous-homogeneous mechanism.
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A number of investigations carried out at the institute was concerned with
the homogeneous stage of the explosive combustion of
presence of hydrogen and methane in the
nitrogen. The relationships which were found brought clarity into
problems connected with the degeneration of the chain mechanism into a thermal
mechanism, the nature of the process of chilling of unstable products, etc.
In a series of investigations the catalytic oxidation of ammonia on plati-
num was studied under dynamic conditions. It was shown that the maxima, which
occur on the cures expressing the dependence of the yield of oxides of nitro-
gen on the time of contact with the catalyst, are produced by the heterogeneous-
homogeneous defixation of ammonia under participation of the walls of the reactor.
In work dealing with the kinetics of polymerization and copolymerization,
data were obtained which indicate that these reactions have a heterogeneous-homo-
geneous character, proceed under particination of the walls of the vessels, and
are of the autocatalytic (explosive) type.
In investigations on the oxidation of propane-butane mixtures conducted at
the institute, it was established that these mixtures do not react when the walls
of the vessel are covered with sodium chloride. Then the conditions necessary
for the initiation of a homogeneous reaction are absent. Later analogous results
were obtafhed at the Institute of Chemical Physics, Academy of Sciences USSR, in
work on the oxidation of propane and at the State Institute of the Nitrogen Indus-
try in work on the oxidation of methane.
The fact that homogeneous stages occur in heterogeneous catalysis was proven
in a series of investigations carried out at the institute, with the aid of the
method of separate calorimetry devised by Koval'skiy at the Institute of Chemi-
cal Physics, Academy of Sciences USSR. As objects of investigation served the
reactions of the incomplete oxidation of methane, ethylene, methanol, and butane-
propane in the presence of platinum, silver, vanadium pentoxide, boron oxide, or
other catalysts covering the walls of the reactors in a thin layer. The experi-
ments confirmed directly the occurence of heterogeneous-homogeneous stages in all
of these catalytic reactions. The specificity of the action of catalysts was ex-
pressed in their capacity to lower the temperature of the reaction and the energy
of activation, and also in their selective effect on the formation of different
intermediate products containing oxygen. V. V. Shalya, T. P. Kornienko, Ya. V.
Zhigaylo, V. I. Urizko, and M. A. Piontkovskaya participated in the work on this
subject.
By 1929, 11. V. Polyakov and others started at the institute a series of in-
vestigations dealing with adsorption phenomena and the preparation of adsorbents
having a predetermined pore structure. In this work the effect of the structure
of the pores on the adsorption properties were studied. Furthermore, methods for
the preparation of silica gels of different porosities were developed. On the ba-
sis of this work, research by I. Ye, Neymark and his group was started in 1944.
Detailed investigation by Neymark,and others, of the structure of many samples of
silica gels, which differed with regard to their preparation, led to a new explana-
tion of the mechanism by which the structure by hydrophilous adsorbents comes into
being. According to this explanation, the porosity of a dry gel is determined by
the degree of compression of the hydrogel during its dehydration. The compression
of the hydrogel is effected by capillary forces, the operation of which depends
principally on the surface tension of the intermicellar liquid. During theproc-
ess of drying, the rigidity of the gel skeleton counteracts the effect of the
capillary forces: This rigidity, in turn, is determined by the hydrophilous qual-
ity of the particles entering into the composition of the gel. On the basis of
these concepts it was possible to develop reproducible methods of preparing gels
that have different types of porosity and obtain new structural types of silica
gels as well as mixed adsorbents, e.g., alumosilica gels, etc. Some of the meth-
ods for the preparation of adsorbents, which had been developed at the institute,
were introduced into industrial practice and are also being used in research work
conducted at the leading USSR laboratories.
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In the work done by Neymark and others more precise methods for investi-
gating the structure of porous adsorbents were developed; a system for the
classification of adsorbents according to structural types was formulated and
developed; the mechanism of the inactivation of adsorbents by heat was clari-
fied; and a number of specific properties of mixed adsorbents were elucidated.
Work on the Chemistry of Isotopes
In 1934, soon after the discovery of deuterium, work on the chemistry of
isotopes was begun at the institute. This work has been continued up to the
present day. A. I. Brodskiy and his collaborators (0. K. Skurre, V. A. Alek-
sandrovich, M. K. Shelud'ko, Ye. I. Dontsova, Zh. N. Shershever, S. G. Demi-
denko, L. V. Korchagin, and others) were the first to obtain pure heavy water
i
These us n the USSR (in 1934) and to prepare concentrated heavy oxygen (in 1937).
Generaletheorydofnfravarious ctionation swasadovvelorednandnchecked experimentally. The
correctness of this theory was confirmed on many experimental examples. In a
number of cases, application of this theory was found to replace to advantage
the cumbersome methods of calculation proposed by foreign scientists. During
1934-1941, some physical constants of heavy water were determined and the ex-
change reactions of hydroen isotopes investigated. Specifically, it was es-
tablished that there is a rapid exchange in amino-groups and in the hydroxyl-
groups of phenols. A statistical theory of the equilibrium distribution of
isotopes was developed for compounds which have several exchangeable atoms in
the molecule.
Considerable attention was paid to the isotopic composition of natural
waters. Many published data which were based exclusively on density measure-
ments were not of much value from the scientific standpoint, because the to-
tal change in the density of water is produced by two independent factors:
the content of deuterium and the content of heavy oxygen. A precise method
was developed at the institute for the separate determination of both heavy
isotopes by means of simultaneous interferometric and density measurements,
the latter with the aid of a float. By means of this method it was estab-
lished that water obtained by the melting of snow has a lowered content of
deuterium in comparison with the waters of rivers, lakes, springs, and the
moisture of the air. On the other hand, the heavy oxygen content of snow
water is normal. The isotopic composition of mountain rivers and mountain
lakes, which are fed directly by melting snow, is the same as that of snow
water. It was further established that river ice, just like artifiLial ice,
has a noraml isotopic composition. These differences in composition, which
are connected with the conditions under which moisture crystallizes in the
atmosphere, have not yet been explained in a satisfactory manner. A study
of arctic waters of which samples were collected by USSR arctic expeditions,
showed that these waters can be divided into several sharply distinct groups,
the isotope composition of which depends on orological conditions and the age
of the ice. The isotope composition rem,ins uniform along sea currents for
thousands of miles.
In 1940, at the initiative of the institute, the first conference in the
USSR on isotopes was held by the Academy of Sciences USSR, under the direction
of V. I. Vernadskiy.
The use of isotopes as tracers in the investigation of the mechanism of
chemical processes and in the study of the structure of molecules was begun in
1939, and resumed era a wider scale in 1945 with the participation of G. P. N1k-
lukhin, I. P. Gragerov, B. A. Geller, A. S. Fomenko, I. A. Makolkin, L. L. Cherv-
yatsova, A. F. Rekasheva, I. I. Kukhtenke, L. V. Sulima, and others, Some re-
arrangements and tautomeric transformations were investigated, and the following
results obtained: the absence of tautomerism in toluene, phosphorous acid, the
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salts of phosphorous acid, and the alkyl esters of phosphorous acid was definitely
proven, and its presence in hypophosphorous acid established. The intramolecular
mechanism of the orthorearrangement of allyl esters (Claisen rearrangement) and
the bimolecular mechanism of the rearrangement of oximes proceeding [by interac-
tion of one molecule of the oxime with one molecule of water] under hydration and
dehydration (Beckmann rearrangement) were established and clarified.
A new type of rearrangement of phenols was discovered which consists in the
intramolecular exchange of hydrogen between the hydroxyl group and the hydrogens
occupying the ortho and pare positions in the nucleus. A systematic investiga-
tion of the reduction of ketones, diazonium salts, and phenyl hydrazine with al-
coholates demonstrated that the reduction is effected by transfer of hydrogen atoms
attached by C-H bonds, rather than the transfer of hydrogen atoms attached b' 0-H
bonds in the hydroxyl groups of the alcohol or water. The exchange of identical
radicals between alkyl halides, ethers, and dimethyl sulfate was investigated.
With the aid of deuterium, the mechanisms of the photochemical and thermal decom-
position of diphenylmercury and phenylmercury hydroxide were compared. This in-
vestigation was carried out in collaboration with Prof G. V. Razuvayev.
Significant results were obtained by using isotopes in research pertaining
to the theory of chemical structure. It was established with the aid of deuterium
that the H-atoms forming the hydrogen bonds in benzoquinhydrons are located at the
hydroquinone nucleus. On heating, there is a tautomeric transformation in the
Course of which the H-atoms forming the bonds are transferred individually to the
quinone nucleus after passing a potential barrier of 30 kilocalories per gram-mol.
The effect of the conjugation of bonds in salts of carboxylic acids was dis-
closed. This effect is expressed in the circumstance that the mobility of alpha-
hydrogen atoms is decreased as the polarity of the 0-X bond (where X stands for a
metal or radical) increases. The application of this effect led to a new variation
of the Perkin reaction carried out without acetic anhydride. If in the hydrogen
exchange by acetates the heavy water is replaced by heavy acetic anhydride, the
effect that has been described is reversed, as can be expected on the basis of
theoretical considerations.
A new general theory of hydrogen exchange in solutions has been developed..
This theory connects the rate of exchange with the structure of the electron shell
of the atom to which the hydrogen being exchanged is bound. This theory was con-
firmed by studying the hydrogen exchange of ammonium salts, phosphates, hypophos-
phites, and also of Si-H groups of orgunosilicon compounds. The use of the heavy
isotopes of hydrogen and oxygen made it possible to establish that there are sig-
nificant differences between the behavior of [purely] organic compounds and that
of the corresponding organosilicon compounds. These differences are due to the
opposite polarities of the C-H and Si-F bonds.
During recent years particular attention was paid to the investigation of
sulfur compounds with the aid of radioactive sulfur. It was established in work
done under participation of G. A. Blokh that acceleration of the vulcanization of
rubber by raptax (e-mercaptobenzothiazole) is brought about by the transfer of sul-
fur originating from exchange in the sulfhydryl group of the Captax accelerator.
This exchange is apparently connected with a tautomeric transformation of the Cap-
tax molecules. Furthermore, the mechanisms of the reactions of the'formation and
decomposition of trithlonates were clarified. This brought clarity to a question
which could not be solved previously by a number of chemists.
It has been established by D. N. Strazhesko's work that electrochemical ad-
sornti.on, i.e., adsorption that does not depend on the sign of the charge at the
sur:'ace of the adsorbent, takes place on carbon not only in water but also in a
number of nonaqueous solvents. This confirmed the applicability of A. N. Frumkin's
electrochemical theory of ionic adsorption to nonaqueous solutions and considerably
extened the field of this theory's application. With the aid of radioactive isotopes
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the fundamental laws of the electrochemical adsorption of.ions from highly diluted
aqueous and nonaqueous solutions were investigated. The results that had been ob-?
tained led to the development of a new method of preparative microchemistry, which
made it possible to solve a number of important problems. Furthermore, the simi-
larity ~Rtween the orientation of polar organic molecules at the surface carbon
and their orientation at other phase boundaries was demonstrated, These investiga-
tions led to the introduction into industrial
technique for the purification of practice of a substantially improved
therapeutic preparations by adsorption.
Work in the Field of Photoehemistr
The photochemical research which was begun at the institute about
Pisarzhevskiy's initiative represented further developement of his ideas on at
on the
electronic mechanism of elementary process of oxidation and reduction. These
ideas received a direct confirmation in work done by B. Ya. Dain and his collab-
orators (M. S. Ashkinazi, T. S. Glikman, A. A. Kachan, B. F. Kutsaya, and others)
on the primary processes which are induced by light quanta in solutions.
The most sifnificant results were obtained in the investigation of photo-
processes taking place in solutions of electrolytes. In this work the specific
type of elementary photochemical process was discovered and investigated in
which electrons are transferred by light quanta from particles of one kind to
particles of anothe.+~ind in the immediate vicinity. This type of light-induced
transfer was invest gated iii detail on the ions C2O42=, Fe2t', and Cr ",
Analysis of the kinetic data pertaining to these processes, as well as of
the regularities in the spectra of the ions involved, indicates that the water
molecules of the hydrate envelope, serve as receptors of the electrons in all
cases. It was shown that the development of hydrogen, which is observed in re-
actions of this type, is a result of the decomposition of the water of the sol-
vent. It was also established that there is a simple relationship between the
position at the end of the long-wave region in the spectra of the electron trans-
mission of ions and the redox potential of the systems under investigation. The
nature of the so-called active oxalic acid was clarified for the first time. In
the light of the data obtained, a general explanation of the volume photogalvanie
effect could be given. This effect is observed specifically in oxalate solutions,
The second type of the photochemical transfer of ele trons was 'tudied after
World War II on ions of' the oxidized type, e.g., Fe34,, Cu ", and cell", It was
established that the action of light quanta on these ions brings about their pho-
tochemical reduction by transfer of electrons to tham from the water molecules,
which decompose under the formation of oxygen. On the example of Ce4? ions, the
effect of the walls of the vessel on the light-induced transfer of electrons was
demonstrated.
The third type of elementary processes of this kind, i.e., processes involv-
ing transfer of eletrons within complexes, was investigated in research on the
photochemistry of complex oxalates. The investigation of the spectra and of' the
photochemical behavior of 12 complex compounds of this class led to the conclusion
that only those in which the transfer of electrons is possible are subjected to
photochemical decomposition. This conclusion has general validity in the photo-
chemistry of complex compounds.
The photochemical reactions which involve electron transfers as.welJ as
the spectra that pertain to these reactions were also investigated on the alco-
hol solutions of a number of salts. On the basis of the relationships which had
been established, a general concept was formed in regard to the dependence of the
position of ion adsorption bands on the donor and acceptor characteristics of the
solvent.
- - - airs
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On the basis of the data obtained in regard to the photoinduced reactions
of electron transfer, it was shown that almost all known reactions which take
place in electrolyte solutions invel-?e transfer of electrons in the primary
stage of the reaction. The same data were used in establishing general rela-
tionships which pertain to the mechanism of redox reactions taking place in
the dark.
With-the purpose of establishing the mechanism of the photochemical redox
transformations that are characteristic for organic systems, in which transfer
of hydrogen is the immediate result of the action of light, the photochemical
reduction of some oxazine and thiazine dyestuffs was investigated and the pho-
tooxidation of their leucoforms was studied. It was established that the proc-
esses involved are subject to general laws which are in agreement with A. N.
Terenin's concept that the photochemical transfer of hydrogen proceeds in two
stages, of which the first stage is the photoinduced transfer of an electron.
It was shown on several examples that introduction of a metal into the mnlp-
cu.les of colored substances (azodyestuffs, pheophytin, and phenoph(rbide)
causes sharp changes of the activity of these substances in photochemical
redox reactions.
When iron salts were reacted with pheophytin or pheophorride, oxidized
and reduced iron-containing analogs of chlorophyll were obtained. These ana-
logs were found to undergo mutual transformation as a result of the action of
quanta of visible light. This result is of interest from the standpoint of the
theory of photosynthesis, because in the organism of plants all prerequisites
exist for the formation of complex compounds of this type, while the mutual
photochemical transformations of these complexes indicate that the transforma-
tions in question may participate in the sensitization leading to reactions,
which occur in the first stage of the photosynthesis.
Work on the Structure of Liquids
From 1927 to 1930, V. I. Danilov, together with A. Z. Golik and others,
began basic research on the structure of liquids, using X-ray methods. Since
1946, Golik has continued this work at the institute.
At present, neither a quantitative theory of the liquid state nor a mole-
cular theory of the viscosity of liquid; exists. Because specific difficul-
ties interfere with the formulation of these theories, a number of physicists
acquired the impression that fundamental obstacles of a theoretical nature
make the formulation of a quant.tative theory of the liquid state impossible.
A new approach to the problem became necessary. This new approach is outlined
in Golik's work, who has advanced the idea of studying the molecular structure
of liquids and the mutual interdependence of the physical properties of matter
in the liquid state.
From this standpoint extensive experimental investigations have been carried
out on the viscosity, density, critical temperatures, latent heats of evapora-
tion, X-ray structure, and the solubility of pure liquids and of their binary
and ternary solutions. The dependence on the molecular structure of the viscos-
ity, density, and critical temperatures of a large number of organic liquids and
their solutions of the molecular mixture type was subjected to study. Solutions
of electrolytes were also investigated from this standpoint. New relationships
were established for the dependence of the properties enumerated on the tempera-
ture and the concentration. It has been found that these properties depend on
the molecular structure.
Analogous investigations were carried out on solutions the components of
which interact chemically with each other. It was established that different,
much more complicated relationships apply to solutions of this type.
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New data were obtained on the structure of liquids and a method was de-
veloped for the calculation of some physical properties of liquids on the
basis of their function of radial distribution.
Collation and evaluation of the results showed that knowledge of the co-
ordination number and of the radius of the first coordination sphere only is
not adequate for the characterization of the structure of a liquid substance:
one must introduce an additional parameter which characterizes the interaction
between molecules and is closely connected with the critical parameters [con-
stants] of the substance. Thus, the critical temperature characterizes macro-
scopically the third parameter, which together with the coordination number
and the radius of the first coordination sphere, determines the structure of
a liquid. The cotcept of the molecular structure of matter in the liquid state
has been introduced, a concept which takes into consideration not only the geo-
metric, but also the dynamic characteristics of the microstructure of a liquid,
i.e., the type of molecular interaction in it. A simple method for characteriz-
ing liquids on the basis of their molecular structure has thus been introduced
and is being applied.
Furthermore, it has been shown that within the limits of classes of liquids
that have a similar molecular structure simple relationships exist which charac-
terize the dependence of physical properties on the temperature and the inter-
dependence of these properties on each other. On the lasis of these considera-
tions, workers at the institute predicted and discovered the existence of the
so-called isoviscous liquids which have different compositions, but an identical
viscosity throughout the whole temperature range of the existence of the liquid
phase.
When the components of a solution differ with respect to their molecular
structure, and particularly when they interact with each other, simple relation-
ships for the dependence of physical properties on the temperature and the con-
centration do not apply, nor are isoviscous liquids formed.
From 1940 to 1948, N. F. Vuks, who studied the Rayleigh dispersion and Raman
dispersion spectra within the low frequencies range in crystals and liquids, ob-
tained proof that the lines of low frequency in spectra of organic crystals are
produced by rotary oscillations of the molecules in the lattice. On the basis
of the correspondence between low frequency spectra of crystals and liquids, the
conclusion was made that the molecular dynamics of liquids are similar to the
dynamics of crystals. Furthermore, a new method was developed for th. investi-
gation of the composition of the Raylet;h emission spectrum and of the low fre-
quency spectrum, namely the method of resonance filtration. This method aided
in obtaining complete data on the distribution of intensities in the region of
the Rayleigh lines of some liquids.
Work in Other Fields
In work done at the institute considerable attention was paid to the appli-
cation of physicochemical methods of analysis in production control.
From 1930 to 1941, A. N. Zan'ko and others, who worked on the theory of
potentiometry, proposed the following methods for practical application at plant
laboratories: a poteatiometric method for the complete analysis of manganese
ores; a polarographic titration method for the determination of magnesium in
dolomites; and rapid methods for the polarographic determination of metals.
Lan'ko and his group carried out a number of investigations on the application
of organic reagents in analysis, and on conductometric and iuterferometric
analysis. With the participation of V. F. Stefanovskiy, the kinetics of rapid
redox reacions were studied.
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From 1937 to 1949, work on physicochemical methods of analysis was also con-
ducted by M. S. Ashki azi. During a number of years she and her collaborators
worked on the development of method for the quantitative analysis of ferrous
metals, nonferrous metals, and alloys by emission spectroscopy. The introduc-
tion of these methods into practical use was expedited during World War II. As
a result of this work, determination of metals with the aid of a single standard
or without a standard became possible, and procedures of this type were adopted
in practical industrial plant control.
Under the direction of A. L. Davydov and with the participation of Z. M.
Vaysberg,-iew, precise, and sensitive photocolorimetric methods for the deter-
mination of phosphorus, vanadium, silicon, tungsten, molybdenum, and arsenic
were developed during 1936-1950. These methods were introduced into practical
use at plant laboratories on a wide scale. Z. M. Vaysberg developed methods
for the determination of columbium and titanium in steels, and of cerium in
minerals. For this purpose the color reactions connected with the formation
of various derivatives of tungsten blue and molybdenum blue were used. To
clarify the chemical nature and structure of these blue compounds, B. Ya Data
and Z. M. Vaysberg subjected them to spectroscopic examination and found that
they belong to a special class of heteropolyacids, which have reduced coordina-
tion groups.
From 1934 to 1941, F. I. Berezovskaya and Ye. K. Varfolomeyeva, who conducted
investigations on the kinetics of reactions in solutions, studied the effect of
various additions on the thermal decomposition of peroxides.
During the postwar years (1944-1949), p. P. Budnikov carried out investiga-
tions on the physical chemistry of silicates. As a result of work done by Budnikov,
a method was developed for the production of gypsum alpha-hemihydrate, a substance high
chanical hich has
as obtainedindex;oandf
method wasstredngth; onfofctrry
tricalcium silicate (alite), a cement which has a very high p mechanical salttrn re^gf
c th.
From 1927 to 1930, G. V. Korshun and K. V. Roll conducted research on the
adsorption spectra of a number of pyrrol derivatives and found that these spectra
depend on the constitution of the compounds in question.
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